Mono and diesters of N-phosphonomethylglycinates as herbicides

ABSTRACT

Alkylphosphonate mono and diesters of N-phosphonomethylglycine are disclosed which are useful as herbicides. This invention further relates to herbicidal compositions containing such alkylphosphonate mono and diesters of N-phosphonomethylglycine and to herbicidal methods employing such compounds and compositions.

This invention relates to mono and diesters ofN-phosphonomethylglycinate which are useful as herbicides. Moreparticularly this invention relates to alkyl phosphonate mono anddiesters of N-phosphonomethylglycinate which are useful as herbicidesand to herbicidal methods employing such compounds and compositions.

U.S. Pat. No. 4,025,331 issued to Jean-Pierre Leber on May 24, 1977discloses N-phosphonomethylglycine derivatives of the formula ##STR1##wherein J is hydrogen, unsubstituted or substituted hydrocarbon or acation and M is hydrogen or a cation. The compounds disclosed in U.S.Pat. No. 4,025,331 supra are said to possess herbicidal and plant growthregulating properties.

The compounds of the present invention are represented by the formula##STR2## wherein R is lower alkyl; R₁ is a (C_(n) H_(2n)) S--X groupwherein X is lower alkyl or lower alkoxycarbonyl and n is an integer offrom 1 to 4; or ##STR3## wherein Z is lower alkyl, and R₂ is hydrogen ora group represented by R₁.

As employed throughout the claims and description, the term "loweralkyl" includes alkyl radicals which have up to four carbon atoms in astraight or branched chain, for example, methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl and t-butyl.

As employed throughout the claims and description, the term "loweralkoxy" includes groups of the aforedefined term "lower alkyl" whichhave one oxygen associated therewith such as methoxy, ethoxy, propoxyand butoxy.

The term "lower alkoxy carbonyl" is employed throughout the claims anddescription to include groups representative of the aforedefined term"lower alkoxy" in combination with a carbonyl group. Suitable examplesof "lower alkoxy carbonyl" groups include methoxycarbonyl,ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl and the like.

In a preferred embodiment, R is preferably ethyl, R₁ is (C_(n)H_(2n))--S--X, ##STR4## when Z is methyl or propyl, and R₂ is preferablyhydrogen or R₁, and n is preferably 2.

In accordance with the present invention alkylphosphonate diesters ofN-phosphonomethylglycinate of the formula ##STR5## may be prepared bysimultaneously reacting a tri-alkylphosphite of the formula

    P--(O--R.sub.1).sub.3                                      (II)

wherein R₁ and R₂ are defined as recited above with water and with1,3,5-tri-(alkoxycarbonylmethyl) hexahydro-1,3,5-triazine (trimer of theSchiff's base of formaldehyde and corresponding alkyl glycinate) of theformula ##STR6## wherein R is as aforedefined to form a crude diestercomposition containing diester product. A purified diester product maybe recovered from the crude diester compositon by employing suitableseparation means as, for example, employing a chromatographic and/ordistillation means having sufficient capability and capacity to effectthe aforedescribed recovery.

The aforedescribed reaction is carried out at a temperature in the rangefrom about 10 to 110 and preferably from about 20° to about 100° C.

In preparing diester compounds of formula (I), the range of reactants isnot narrowly critical. Preferably, however for each mole oftrialkylphosphite employed, one should employ from about 0.5 to about1.5 mole water, about 1/4 to about 1/2 mole1,3,5-tri-(alkoxycarbonylmethyl)hexahydro-1,3,5-triazine (which isequivalent to 1 mole of the monomer of a Schiff's base of formaldehydeand the corresponding alkyl glycinate) while no catalyst is required forthe aforedescribed reaction to proceed although a catalyst may beemployed if desired.

The reaction time is in the range from about 1 to about 72 and ispreferably from about 2 to about 50 hours.

While the process of this invention can be conducted at atmospheric,sub-atmospheric or super-atmospheric pressure, for convenience andeconomy it is generally preferred to conduct these processes atatmospheric pressure.

Although a suitable solvent may be employed in the aforedescribedprocess, it is preferred that the reaction be carried out in the absenceof a solvent.

Suitable agitation is provided, preferably by stirring or otherwiseagitating the reaction composition.

In practicing the aforedescribed process the aforedescribed reactantsare admixed together although the reactants may be admixed in any orderif desired to form a reaction composition.

In another embodiment of this invention the aforedescribed diestercompounds of formula (I) may be prepared by reacting a disubstitutedphosphite of the formula ##STR7## with the aforedescribed trimer offormula (I). Typically a coproduct alcohol compound formed whenemploying a triphosphite and water as reactants along with said trimeris not believed formed in this embodiment.

The ratio of reactants, disubstituted phosphite and trimer, are notnarrowly critical. Preferably, for each mole of diphosphite employed,one should employ about 1/4 to about 1/2 mole trimer of formula (I).

The aforedescribed conditions of pressure, agitation and admixingdiscussed with respect to use of tri-substituted phosphite, water andtrimer apply generally with respect to this embodiment as well.

The temperature employed for this embodiment is generally in the rangefrom about 90° to about 110° C. and the reaction time is generally inthe range from about 1 to about 6 hours.

The following examples are presented to define the invention morecompletely without any intention of being limited thereby. All parts andpercentages are by weight, unless otherwise specified.

EXAMPLE 1

A reaction composition comprising 15.0 g (0.031 mole)tri-[[(2-ethoxycarbonyl)thio]ethyl]phosphite, 0.56 g (0.031 mole) water,and 3.59 g (0.0104 mole)1,3,5-tri(ethoxycarbonylmethyl)hexahydro-1,3,5-triazine was heated atabout 100° to about 110° C. for 3 hours with agitation. An alcohol2-(ethoxycarbonylthio)ethanol co-product was removed by bulb to bulbdistillation of the reaction mixture at 75° C. and 0.05 mmHg. Thedistillation residue was chromatographed on silica gel with ethylacetate eluent. The product, glycine,N-[[bis[2-[(ethoxycarbonyl)thio]ethoxy]-phosphinyl]methyl]-, ethyl esterwas obtained as a viscous yellow oil in 52% yield (7.4 g) having thefollowing analysis:

Calculated: C, 39.04; H, 6.12; N, 3.04; P, 6.71; found: C, 38.16; H,6.16; N, 2.66; P, 6.20.

EXAMPLE 2

A reaction composition comprising 9.6 g (0.025 mole)tri-(tetrahydro-2H-thiopyran-3-yl)phosphite, 0.45 g (0.025 mole) water,and 2.9 g (0.008 mole)1,3,5-tri(ethoxycarbonylmethyl)hexahydro-1,3,5-triazine was heated atabout 100° to about 110° C. for 11/2 hours with agitation. An alcoholtetrahydro-2H-thiopyran-3-ol co-product was removed by bulb to bulbdistillation of the reaction mixture at 120° C. and 0.07 mmHg. Thedistillation residue was chromatographed on microcrystalline cellulosewith an eluent of ethyl acetate/cyclohexane (2:3). The product, glycine,N-[[bis[(tetrahydro-2H-thiopyran-3-yl)-oxy]-phosphinyl]methyl]-, ethylester was obtained as a viscous yellow oil in 40% yield (4.0 g) havingthe following analysis:

Calculated: C, 45.33; H, 7.10; N, 3.52; P, 7.79; S, 16.13; found: C,45.49; H, 7.28; N, 3.52; P, 7.60; S, 16.31.

EXAMPLE 3

A reaction composition comprising 10.4 g (0.04 mole)di-[(2-ethylthioethyl)phosphite], and 4.6 g (0.013 mole)1,3,5-tri(ethoxycarbonymethyl)hexahydro-1,3,5-triazine was heated atabout 100° to about 110° C. for 45 minutes with agitation. The reactionmixture was dissolved in ethyl acetate with formation of a precipitateupon agitating at about 25° C. for 12 hours. Solid was collected andfiltrate concentrated to about 50 ml. The filtrate was chromatographedon microcrystalline cellulose with an eluent of ethylacetate/cyclohexane (1:3) to yield 4.8 g (32%) of the product, glycine,N-[[bis[2-(ethylthio)ethoxy]phosphinyl]methyl]-, ethyl ester having thefollowing analysis:

Calculated: C, 41.81; H, 7.56; N, 3.75; P, 8.29; S, 17.17; found: C,41.96; H, 7.87; N, 3.93; P, 7.99; S, 16.87.

EXAMPLE 4

A reaction composition comprising 10.4 g (0.04 mole)di-[(2-ethylthioethyl)phosphite], and 4.6 g (0.013 mole)1,3,5-tri(ethoxycarbonylmethyl)hexahydro-1,3,5-triazine was heated atabout 100° to 110° C. for 45 minutes with agitation. The reactionmixture was dissolved in ethyl acetate (100 ml) with formation of aprecipitate upon agitating at about 25° C. for 12 hours. Solid wascollected and dried to yield 1.2 g (10.5%) of the product glycine,N-[[[2-(ethylthio)ethoxy]hydroxyphosphinyl]methyl]-, ethyl ester havingthe following analysis:

Calculated: C, 37.89; H, 7.07; N, 4.91; P, 10.86; S, 11.24; found: C,37.85; H, 7.21; N, 4.87; P, 10.90; S, 11.15.

EXAMPLE 5

A reaction composition comprising 5.0 g (0.013 mole)di-[1-(tetrahydro-2-thienyl)ethyl]phosphite-S,S-dioxide and 1.54 g(0.005 mole) 1,3,5-tri(ethoxycarbonylmethyl)hexahydro-1,3,5-triazine washeated at about 100° to 110° C. for 1.5 hours with agitation. Thereaction mixture was dissolved in 25 ml of ethyl acetate andchromatographed on silica gel with ethyl acetate eluent to yield 1 g(15.7%) of the product, glycine,N-[[[bis[1-(tetrahydro-2-thienyl)ethoxy]]phosphinyl], methyl]-, ethylester, S,S,S',S'-tetraoxide having the following analysis:

Calculated: C, 41.71; H, 6.59; N, 2.86; P, 6.33; found: C, 41.82; H,6.53; N, 2.54; P, 6.02.

EXAMPLE 6

A reaction composition comprising 8.1 g (0.018 mole)di-[1-(1-tetrahydrothien-2-yl)butyl]phosphite-S,S-dioxide and 2.2 g(0.006 mole) 1,3,5-tri(ethoxycarbonylmethyl)hexahydro-1,3,5-triazine washeated at about 100° to about 110° C. for 2.5 hours with agitation. Thereaction mixture was dissolved in 25 ml of ethyl acetate andchromatographed on silica gel with ethyl acetate eluent to yield 0.8 g(8%) of the product, glycine,N-[[bis[1-(tetrahydro-2-thienyl)butoxy]]phosphinyl]methyl-, ethyl ester,S,S,S',S'-tetraoxide having the following analysis:

Calculated: C, 46.23; H, 7.39; N, 2.57; P, 5.68; S, 11.75; found: C,46.23; H, 7.59; N, 2.19; P, 5.07; S, 11.55.

EXAMPLE 7

The post-emergent herbicidal activity of some of the various compoundsof this invention was demonstrated by greenhouse testing in thefollowing manner. A good grade of top soil is placed in aluminum panshaving holes in the bottom and compacted to a depth of 0.95 to 1.27 cm.from the top of the pan. A predetermined number of seeds of each ofseveral dicotyledonous and monocotyledonous annual plant species and/orvegetative propagules for the perennial plant species were placed on thesoil and pressed into the soil surface. The seeds and/or vegetativepropagules are covered with soil and leveled. The pans are then placedon a sand bench in the greenhouse and watered from below as needed.After the plants reach the desired age (two to three weeks), each panexcept for the control pans is removed individually to a sprayingchamber and sprayed by means of an atomizer operating at a positive airpressure of approximately 1.46 kg/cm² absolute. The atomizer contains 6ml. of a solution or suspension of the chemical. In that 6 ml., is anamount of a cyclohexanone emulsifying agent mixture to give a spraysolution or suspensin which contains about 0.4% by weight of theemulsifier. The spray solution or suspension contains a sufficientamount of the candidate chemical in order to give application ratescorresponding to those set forth in the tables. The spray solution isprepared by taking an aliquot of a 1.0% by weight stock solution orsuspension of the candidate chemical in an organic solvent such asacetone or tetrahydrofuran or in water. The emulsifying agent employedis a mixture comprising 35 weight percent butylamine dodecylbenzenesulfonate and 65 weight percent of a tall oil ethylene oxide condensatehaving about 11 moles of ethylene oxide per mole of tall oil. The pansare returned to the greenhouse and watered as before and the injury tothe plants as compared to the control is observed at approximately twoand four weeks as indicated in the tables under WAT and the resultsrecorded. In some instances, the two-week observations are omitted.

The post-emergent herbicidal activity index used in Tables I and II isas follows:

    ______________________________________                                        Plant Response  Index                                                         ______________________________________                                        0-24% control   0                                                             25-49% control  1                                                             50-74% control  2                                                             75-99% control  3                                                             100% control    4                                                             ______________________________________                                    

The plant species utilized in these tests are identified by letter inaccordance with the following legend:

    ______________________________________                                        A--Canada Thistle*  K--Barnyardgrass                                          B--Cocklebur        L--Soybean                                                C--Velvetleaf       M--Sugar Beet                                             D--Morningglory     N--Wheat                                                  E--Lambsquarters    O--Rice                                                   F--Smartweed        P--Sorghum                                                G--Yellow Nutsedge* Q--Wild Buckwheat                                         H--Quackgrass*      R--Hemp Sesbania                                          I--Johnsongrass*    S--Panicum Spp                                            J--Downy Brome      T--Crabgrass                                              ______________________________________                                         *Established from vegetative propagules.                                 

                                      TABLE I                                     __________________________________________________________________________    Compound of    Plant Species                                                  Example No.                                                                          WAT  kg/h                                                                             A  B C  D E F G H I J K                                        __________________________________________________________________________    1      4    11.2                                                                             2  2 0  2 0 1 1 1 2 0 2                                               4    5.6                                                                              1  0 0  2 0 0 0 0 1 0 1                                        2      4    11.2                                                                             0  0 1  1 1 0 0 1 0 0 1                                               2    5.6                                                                              0  0 0  0 0 0 0 0 0 0 0                                        3      4    11.2                                                                             1  1 0  1 0 0 1 1 3 0 2                                               4    5.6                                                                              1  1 0  1 0 0 1 0 0 0 2                                        4      4    11.2                                                                             4  4 3  3 3 4 0 3 4 2 4                                               4    5.6                                                                              2  2 4  2 0 3 1 3 4 2 4                                        5      2    11.2                                                                             0  0 0  0 0 0 0 0 0 0 0                                               2    56.0                                                                             0  1 0  1 1 1 0 0 0 0 0                                               4    56.0                                                                             0  1 0  1 0 1 0 0 1 0 0                                        6      2    11.2                                                                             0  0 0  0 0 1 0 0 1 0 0                                               2    5.6                                                                              0  0 0  0 0 0 0 0 1 0 0                                        __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________    Compound of   Plant Species                                                   Example No.                                                                          WAT kg/h                                                                             L M N O P B Q D R E F C J S K T                                 __________________________________________________________________________    4      4   5.6                                                                              3 --                                                                              4 3 4 4 3 4 4 4 4 4 4 4 3 3                                        4   1.12                                                                             1 4 1 1 3 3 2 2 4 1 4 1 3 4 2 2                                        4   0.28                                                                             0 1 0 1 1 0 1 0 2 3 0 0 0 2 1 2                                 __________________________________________________________________________

From the test results presented in Tables I and II, it can be seen thatthe post-emergent herbicidal activity of the compounds of this invetionis, for the most part, general in nature. In certain specific instances,however, some selectivity is demonstrated. In this regard it should berecognized that each individual species selected for the above tests isa representative member of a recognized family of plant species.

The herbicidal compositions, including concentrates which requiredilution prior to application to the plants, of this invention containfrom 5 to 95 parts by weight of at least one compound of this inventionand from 5 to 95 parts by weight of an adjuvant in liquid or solid form,for example from about 0.25 to 25 parts by weight of wetting agent, fromabout 0.25 to 25 parts by weight of a dispersant and from 4.5 to about94.5 parts by weight of inert liquid extender, e.g., water, acetone,tetrahydrofuran, all parts being by weight of the total composition.Preferably, the compositions of this invention contain from 5 to 75parts by weight of at least one compound of this invention, togetherwith the adjuvants. Where required, from about 0.1 to 2.0 parts byweight of the inert liquid extender can be replaced by a corrosioninhibitor such as ethanol mercaptan, sodium thiosulfate, dodecylmono ordimercaptan or anti-foaming agent such as dimethylpolysiloxane, or both.The compositions are prepared by admixing the active ingredient with anadjuvant including diluents, extenders, carriers and conditioning agentsto provide compositions in the form of finely-divided particulatesolids, pellets, solutions, dispersions or emulsions. Thus, the activeingredient can be used with an adjuvant such as a finely-divided solid,a liquid of organic origin, water, a wetting agent, a dispersing agent,an emulsifying agent or any suitable combination of these.

The herbicidal compositions of this invention, particularly liquids andsoluble powders, preferably contain as a conditioning agent one or moresurface-active agents in amounts sufficient to render a givencomposition readily dispersible in water or in oil. The incorporation ofa surface-active agent into the compositions greatly enhances theirefficacy. By the term "surface-active agent," it is understood thatwetting agents, dispersing agents, suspending agents and emulsifyingagents are included therein. Anionic, cationic and nonionic agents canbe used with equal facility.

Preferred wetting agents are alkyl benzene and alkyl naphthalenesulfonates, sulfated fatty alcohols, amines or acid amides, long chainacid esters of sodium isothionate, esters of sodium sulfosuccinate,sulfated or sulfonated fatty acid esters petroleum sulfonates,sulfonated vegetable oils, polyoxyethylene derivatives of phenols andalkylphenols (particularly isooctylphenol and nonylphenol) andpolyoxyethylene derivatives of the mono-higher fatty acid esters ofhexitol anhydrides (e.g., sorbitan). Preferred dispersants are methylcellulose, polyvinyl alcohol, sodium lignin, sulfonates, polymeric alkylnaphthalene sulfonates, sodium naphthalene sulfonate, polymethylenebisnaphthalenesulfonate and sodium N-metyl-N-(long chain acid) taurates.

The following list gives some specific herbicidal compositions of thisinvention. It is to be realized that the solvents and surfactants areinterchangeable in the composition.

    ______________________________________                                        1.      Glycine, N--[[bis[2-[ethoxycarbonyl)-                                                                95    parts                                            thio]ethoxy]phosphinyl]methyl]-,                                              ethyl ester                                                                   Methanol               5     parts                                    2.      Glycine, N--[[bis[2-(ethylthio)-                                                                     95    parts                                            ethoxy]phosphinyl]methyl]-, ethyl                                             ester                                                                         Ethoxylated nonyl phenol                                                                             5     parts                                    3.      Glycine, N--[[bis[(tetrahydro-2H--                                                                   90    parts                                            thiopyran-3-yl)oxy]phosphinyl]-                                               methyl-, ethyl ester                                                          Isopropanol            10    parts                                    4.      Glycine, N--[[bis[1-(tetrahydro-                                                                     90    parts                                            2-thienyl)ethoxy]]phosphinyl]-                                                methyl]-, ethyl ester, S,S--dioxide                                           Ethoxylated octyl phenol                                                                             10    parts                                    5.      Glycine, N--[bis-1-(1-(2-tetra-                                                                      90    parts                                            hydrothenyl-1,1-dioxide)butyl)-                                               phosphinylmethyl]-, ethyl ester                                               Chloroform             5     parts                                            Ethoxylated dinonyl phenol                                                                           5     parts                                    6.      Glycine, N--[[bis[2-[ethoxycarbonyl)-                                                                75    parts                                            thio]ethoxy]phosphinyl]methyl]-,                                              ethyl ester                                                                   Butanol                25    parts                                    7.      Glycine, N--[[bis[(tetrahydro-2H--                                                                   75    parts                                            thiopyran-3-yl)oxy]phosphinyl]-                                               methyl-, ethyl ester                                                          Ethoxylated oleyl alcohol                                                                            25    parts                                    8.      Glycine, N--[[bis[2-(ethylthio)-                                                                     75    parts                                            ethoxy]phosphinyl]methyl]-, ethyl                                             ester                                                                         Acetonitrile           15    parts                                            Ethoxylated cocoamine  10    parts                                    9.      Glycine, N--[[[2-(ethylthio)ethoxy]-                                                                 75    parts                                            hydroxyphosphinyl]methyl]-, ethyl                                             ester                                                                         Ethyl acetate          20    parts                                            Ethoxylated tallow amine                                                                             5     parts                                    10.     Glycine, N--[[bis[2-[ethoxycarbonyl)-                                                                50    parts                                            thio]ethoxy]phosphinyl]methyl]-,                                              ethyl ester                                                                   Dimethylformamide      50    parts                                    11.     Glycine, N--[[bis[(tetrahydro-2H--                                                                   50    parts                                            thiopyran-3-yl)oxy]phosphinyl]-                                               methyl-, ethyl ester                                                          Isopropyl dodecylbenzene sulfonate                                                                   50    parts                                    12.     Glycine, N--[[bis[2-[ethoxycarbonyl)-                                                                50    parts                                            thio]ethoxy]phosphinyl]methyl]-,                                              ethyl ester                                                                   Dimethylsulfoxide      40    parts                                            Ethoxylated soybeanamine                                                                             10    parts                                    13.     Glycine, N--[[[2-(ethylthio)ethoxy]-                                                                 50    parts                                            hydroxyphosphinyl]methyl]-, ethyl                                             ester                                                                         α-butyrolactone  25    parts                                            Triethanolamine dodecylbenzene                                                                       25    parts                                            sulfonate                                                             14.     Glycine, N--[[bis[(tetrahydro-2H--                                                                   50    parts                                            thiopyran-3-yl)oxy]phosphinyl]-                                               methyl, ethyl ester                                                           1,1,1-Trichloroethane  42    parts                                            Ethoxylated nonyl phenol                                                                             8     parts                                    15.     Glycine, N--[[[2-(ethylthio)ethoxy]-                                                                 25    parts                                            hydroxyphosphinyl]methyl]-, ethyl                                             ester                                                                         Chloroform             75    parts                                    16.     Glycine, N--[[[bis[1-(tetrahydro-                                                                    25    parts                                            2-thienyl)ethoxy]]phosphinyl]-                                                methyl]-, ethyl ester, S,S-- dioxide                                          Chloroform             70    parts                                            Ethoxylated tallow amine                                                                             5     parts                                    17.     Glycine, N--[bis-1-(1-(2-tetra-                                                                      25    parts                                            hydrothenyl-1,1-dioxide)butyl)-                                               phosphinylmethyl]-, ethyl ester                                               1,1,1-Trichloroethane  74    parts                                            Ethoxylated oleyl alcohol                                                                            1     part                                     18.     Glycine, N--[[bis[2-[ethoxycarbonyl)-                                                                25    parts                                            thio]ethoxy]phosphinyl]methyl]-,                                              ethyl ester                                                                   Chloroform             68    parts                                            Ethoxylated dinonyl phenol                                                                           7     parts                                    19.     Glycine, N--[[[2-(ethylthio)ethoxy]-                                                                 10    parts                                            hydroxyphosphinyl]methyl]-, ethyl                                             ester                                                                         Chloroform             90    parts                                    20.     Glycine, N--[[bis[2-[ethoxycarbonyl)-                                                                10    parts                                            thio]ethoxy]phosphinyl]methyl]-,                                              ethyl ester                                                                   Methanol               80    parts                                            Polyoxypropylene - polyoxyethylene                                                                   10    parts                                            block copolymer                                                       21.     Glycine, N--[[bis[2-[ethoxycarbonyl)-                                                                10    parts                                            thio]ethoxy]phosphinyl]methyl]-,                                              ethyl ester                                                                   Ethanol                88    parts                                            Polyoxyethylene (20) sorbitan-                                                                       2     parts                                            monolaurate                                                           22.     Glycine, N--[[bis[2-[ethoxycarbonyl)-                                                                10    parts                                            thio]ethoxy]phosphinyl]methyl]-,                                              ethyl ester                                                                   Isopropanol            72    parts                                            Polyoxyethylene sorbitan-                                                                            18    parts                                            monooleate                                                            23.     Glycine, N--[[bis[2-[ethoxycarbonyl)-                                                                5     parts                                            thio]ethoxy]phosphinyl]methyl]-,                                              ethyl ester                                                                   Dimethylformamide      95    parts                                    24.     Glycine, N--[[bis[2-(ethylthio)-                                                                     5     parts                                            ethoxy]phosphinyl]methyl]-, ethyl                                             ester                                                                         Acetonitrile           90    parts                                            Ethoxylated tallow amine                                                                             5     parts                                    25.     Glycine, N--[[[bis[1-(tetrahydro-                                                                    5     parts                                            2-thienyl)ethoxy]]phosphinyl]-                                                methyl]-, ethyl ester, S,S--dioxide                                           Ethanol                94    parts                                            Ethoxylated tallow amine                                                                             1     part                                     26.     Glycine, N--[bis-1-(1-(2-tetra-                                                                      5     parts                                            hydrothenyl-1,1-dioxide)butyl)-                                               phosphinylmethyl]-, ethyl ester                                               Isopropanol            80    parts                                            Ethoxylated cocoamine  15    parts                                    ______________________________________                                    

When operating in accordance with the present invention, effectiveamounts of the compounds or compositions of this invention are appliedto the plants, or to soil containing the plants, or are incorporatedinto aquatic media in any convenient fashion. The application of liquidand particulate solid compositions to plants or soil can be carried outby conventional methods, e.g., power dusters, boom and hand sprayers andspray dusters. The compositions can also be applied from airplanes as adust or a spray because of their effectiveness at low dosages. Theapplication of herbicidal compositions to aquatic plants is usuallycarried out by adding the compositions to the aquatic media in the areawhere control of the aquatic plants is desired.

The application of an effective amount of the compounds or compositionsof this invention to the plant is essential and critical for thepractice of the present invention. The exact amount of active ingredientto be employed is dependent upon the response desired in the plant aswell as such other factors as the plant species and stage of developmentthereof, and the amount of rainfall as well as the specific glycineemployed. In foliar treatment for the control of vegetative growth, theactive ingredients are applied in amounts from about 0.112 to about 56.0or more kilograms per hectare. In pre-emergent treatments, the rate ofapplcation can be from about 0.56 to about 22.4 or more kilograms perhectare. In applications for the control of aquatic plants, the activeingredients are applied in amounts of from about 0.01 parts per millionto about 1000 parts per million, based on the aquatic medium. Aneffective amount for phytotoxic or herbicidal control is that amountnecessary for overall or selective control, i.e., a phytotoxic orherbicidal amount. It is believed that one skilled in the art canreadily determine from the teachings of this specification, includingexamples, the approximate application rate.

There are several methods for applying liquid compositions of thisinvention to emerged plants. Such methods include the use of wipersystems whereby the plant to be treated is contacted with an absorbentmaterial containing the particular liquid composition, a portion ofwhich is thereby released onto the plant upon contact therewith. Suchwiper systems typically comprise a reservoir of the liquid compositioninto which a portion of the absorbent material is placed and is fedtherethrough. Generally, substances employable as absorbent materialinclude substances of any shape or form capable of absorbing the liquidcomposition and releasing a portion of the same upon contact with theplant. Typical absorbent materials include felt, foam rubber, cellulose,nylon, sponges, hemp, cotton, burlap, polyester over acrylic,combinations thereof and the like. Forms of absorbent material includerope, twine, string, cloths, carpets, combinations thereof and the like.These forms may be assembled in any manner desired including a pipe ropewick, a wedge rope wick, a multi-rope wick and the like.

In another application method, liquid compositions may be selectivelyapplied to weeds by the use of recirculating sprayer systems wherein therecirculating spray unit is mounted on a tractor or high clearancemobile equipment and the spray is directed horizontally onto the weedsgrowing over a crop. Spray not intercepted by the weeds is collected ina recovery chamber before contacting the crop and is reused. Rollerapplications may also be employed to apply liquid compositions to weedsgrowing over a crop.

In yet another application method, shielded applicators may be employedto direct the liquid composition in the form of a spray onto the weedswhile effectively shielding the crops from the spray.

These and other application methods for selectively applying liquidcompositions to weeds are discussed in detail in Innovative Methods ofPost-Emergence Weed Control, McWhorter C. G., Southern Weed ScienceSociety, 33rd Annual Meeting Proceedings, Jan. 15-17, 1980; AuburnUniversity Printing Service, Auburn, Ala. U.S.A., the teachings of whichare incorporated herein by reference in their entirety.

Another method of applying liquid compositions of this invention toplants include controlled droplet application which is also known as theultra low-volume chemical application. Controlled droplet applicationinvolves the production of uniform or nearly uniform spray drops of apredetermined size and the conveyance of these drops with negligibleevaporation to a spray target. In particular, this method comprisesfeeding spray solutions to a rotary atomizer comprising a small diskwith serrated edges that disperses liquid into droplets as the diskspins. Different droplet sizes are produced by changing solution flowrates to the spinning disk or changing the speed of rotation of thedisk.

The aforementioned and other methods for applying liquid compositions toplants are discussed in detail in "Rope Wick Applicator--Tool With AFuture," Dale, James E., pp. 3-4, "The Recirculating Sprayer andRoundup® Herbicide," Derting, Claude W., pp. 5-7, and "C.D.A. HerbicideApplication," McGarvey, Frank X., Weeds Today, Volume 11, Number 2, pp.8-9, Late Spring, 1980, 309 W. Clark St., Champaign, Ill., the teachingsof which are incorporated herein by reference in their entirety.

Although this invention has been described with respect to specificmodifications, the details thereof are not to be construed aslimitations, for it will be apparent that various equivalents, changesand modifications may be resorted to without departing from the spiritand scope thereof and it is understood that such equivalent embodimentsare intended to be included herein.

What is claimed is:
 1. Alkylphosphonate diesters ofN-phosphono-methylglycinate of the formula ##STR8## wherein X is ethylor ##STR9## and R₂ is hydrogen or --C_(n) H_(2n) --S--X), n is aninteger of 1 to
 4. 2. A compound of claim 1, wherein n is 2 and R₂ is--C₂ H₄ S--X).
 3. A compound of claim 2, wherein R₂ is hydrogen.
 4. Acompound of claim 1, wherein R₂ is --(C_(n) H_(2n))--S--X, wherein n is2 and wherein X is ethyl or ##STR10##
 5. A herbicidal compositioncomprising a herbicidally effective amount of a compound of claim 1,together with an inert diluent.
 6. A herbicidal composition comprising aherbicidally effective amount of a compound of claim 2, together with aninert diluent.
 7. A herbicidal composition comprising a herbicidallyeffective amount of a compound of claim 3, together with an inertdiluent.
 8. A herbicidal composition comprising a herbicidally effectiveamount of a compound of claim 4, together with an inert diluent.
 9. Aherbicidal method which comprises contacting a plant with a herbicidallyeffective amount of a compound of claim
 1. 10. A herbicidal method whichcomprises contacting a plant with a herbicidally effective amount of acompound of claim
 2. 11. A herbicidal method which comprises contactinga plant with a herbicidally effective amount of a compound of claim 3.12. A herbicidal method which comprises contacting a plant with aherbicidally effective amount of a compound of claim 4.